DE2157207A1 - Grease - Google Patents

Description

Grease

The invention "relates to an improved lithium soap grease of first quality; with outstanding properties that can be found in a high drip point, excellent resistance to oxidation, long lubrication times and water resistance.

Lithium greases are known and have been used extensively for many years. The lithium soaps used for such fats as Thickeners used are usually due to Reacting lithium hydroxide or another suitable lithium base with a customary high molecular acid or produced several acids. The main advantages of lithium greases are their high water resistance and the ease of dispersing these soaps in all types of oil-based lubricants. Particularly useful are fats made from lithium hydroxystearate, as the soaps are made from hydroxystearic acid and related hydrosy-

209322/0919

Fatty acids have proven to be mechanically more stable than that corresponding soaps of common fatty acids.

There are numerous uses for grease compositions where a high dropping point is required, such as P for lubricating tractor engine bearings. Such traction motors are used to drive modern diesel locomotives. The bearings of such locomotives should work for a period of more than 3 years without maintenance and temperatures of up to 121 ⁰ O can occur in such bearings.

According to the present invention, a lithium base grease which is excellent in oxidation resistance and mechanical strength is obtained and has a dropping point of 26o ° C higher, made from the following ingredients: (a) a 9-hydroxy, lo-hydroxy or 12-hydroxy fatty acid with 12 to 24, preferably 16 to 20 carbon atoms in the molecule, (b) a second hydroxycarboxylic acid with 3 to 14 carbon atoms in the molecule in which the hydroxyl group sits on a carbon atom that is no longer than 6 carbon atoms away from the carboxyl group and (c; a dicarboxylic acid with 4 to 12 carbon atoms in the molecule or boric acid.

In the American patent 2,94o, yjo it is already stated that fats with a high dropping point of 26o ° C or higher are made from mixtures of monocarboxylic and dicarboxylic acids can be. However, it was necessary to use glycol in the manufacture of the fats described in this patent. The presence Glycol is undesirable as it makes the fat sensitive to oxidation makes and reduces the water resistance of the grease in various applications to an undesirable extent. The present Invention enables the production of fats with high drip -3-

209822/0919

point from a combination of hydroxy fatty acid and aliphatic Dicarboxylic acids without the need to incorporate glycol into the mass.

American patents 3,223,633 and 3,223,624 teach the manufacture of fats with a high dropping point from a 3-component mixture of acids. The presence of fatty acid salts with 2 However, up to 4 carbon atoms in the molecule, which are an essential component of such fats, is often undesirable because such fats show a tendency to harden the surface on standing.

The hydroxy fatty acid used in the production of fats according to the invention has about 12 to 24, preferably 6 to 2o, Carbon atoms in the molecule and is preferably a hydroxystearic acid, for example γ-hydroxy, 10-hydroxy or 12-hydroxystearic acid, Also hicinoleic acid, which is an unsaturated form of 12-hydroxystearic acid and in the 9-io position has a double bond can be used.

The hydroxycarboxylic acid, which is the second component of the fat according to the invention, is one in which the hydroxyl group on a carbon atom that is not more than 6 carbon atoms away from the carboxyl group. This acid has 3 to 14 carbon atoms in the molecule and can either an aliphatic acid such as lactic acid, 6-hydroxy decanolic acid, 3-hydroxybutanolic acid, 4-hydroxybutanolic acid and the like, or an aromatic acid such as parahydroxybenzoic acid, salicylic acid, 2-Hydroxy-4-hexylbenzoic acid, meta-hydroxybenzoic acid, 2,2-dihydroxy-benzoic acid (.Gentisic acid, 2,6-dihydroxybenzoic acid (.Garoma-isorcic acid.), 4-hydroxy-3-methoxybenzoic acid and others. or

209822/0919

be a hydroxyaromatic aliphatic acid, such as orthohydroxyphenyl-, Meta-hydroxyphenyl or i'arahydroxyphenylacetic acid; also, a cycloaliphatic hydroxy acid such as hydroxy cyclopentyl carboxylic acid or hydroxynaphthalic acid can be used.

In the production of the .Fettes, instead of a free hydroxy acid of the last-mentioned type, an ester of a lower alcohol, for example the methyl, ethyl, jfropyl, isopropyl or secondary bytyl ester, of the acid can be used, such as methyl salicylate, in order to treat insoluble Salt to achieve better dispersion. The amount of the lithium salt of the hydroxy acid is between about 0.1 to about 10 % by weight of the finished i'ett, preferably between about 0.5 and about 5

i) the third component is either boric acid or a dicarboxylic acid.

Me dicarboxylic acid should contain U to 12 carbon atoms, preferably b to 10 carbon atoms, in the molecule. Such acids W include succinic acid, glutaric acid, adipic acid, chloric acid, ipimilic acid, azelaic acid, iodecanolic acid, and sebacic acid. Sebacic acid and azelaic acid are preferred.

The total soap and salt content of the Jj'ette is in the order of magnitude of about Z to 3o ü-ew .- #>, preferably between about 5 and 2o (iew.-i &.

If a KicarDonic acid is used, the ratio is up of the hydroxy fatty acid with 12 to 24 carbon atoms in the molecule to the icarboxylic acid in the order of magnitude of c, 5 to 15 'aew the former to 1 part by weight of the latter, ----- ^ - fs wise in -> -

V D 9 3 2 2/0 9 1 9

ORIG / NAL INSPECTED

of the order of 1.5 "to 5% by weight of the hydroxy fatty acid to 1 part by weight of the dicarboxylic acid. The ratio of the second hydroxycarboxylic acid to the dicarboxylic acid is in the order of magnitude of about 0.025 "to 2.5 parts by weight of the former to 1 part by weight of the latter, preferably between 0.125 to 1.25 parts by weight of the the former to 1 part by weight of the latter.

One can also get a high drip point fat by using the monolithium salt of .boric acid instead of the dilithium salt of Dicarboxylic acid is used. If the fat contains .boric acid instead of a Dicarboxylic acid is produced, the weight ratio is between about 3 and. 100 parts by weight or usually between 5 and 8o Parts by weight of the hydroxy fatty acid to 1 part by weight of the boric acid and at a weight ratio of about 0.1 to 10 or better 0.5 to about 5 parts by weight of the second hydroxycarboxylic acid

1 part by weight of the boric acid.

The lubricating oil base used in the preparation of the jetted masses according to the invention can be any conventional mineral oil, a synthetic hydrocarbon oil or a synthetic oil ester. In general, these should üle a viscosity within the range of 35 to 2oo SUS at 99 ⁰ G possess. The lubricating oils that can be used include esters of 2-basic acids, such as di-2-ethylhexyl sebacate, esters of glycol, such as a diester of an uxo acid with 13 carbon atoms, iron tetraethyl glycol, or complex esters, e.g. those obtained by reacting one mole of sebacic acid with 2 moles of tetraethyl englycol or

2 moles of 2-ethylhexanol acid are formed. As other synthetic Synthetic hydrocarbons such as alkylbenzenes, for example the sulylated residues from the alkylation, can also be used of benzene with l'etrapropylene, or copolymers of -6-

209822/0919

Ethylene and propylene are used, and also silicone oils, such as ethylphenylpolysiloxane, We thylpoly siloxane lind The like, also polyglycol oils, for example those obtained by condensation of butyl alcohol with propylene oxide are, also carbonate esters, for example the product of a Reaction of a üxo alcohol containing 8 carbon atoms with Ethyl carbonate with the formation of a half ester, followed by the reaction of the latter with tetraethylene glycol and like; other suitable synthetic oils are polyphenyl ether, for example those that have 3 to 7 ither bonds and have about 4 to 8 phenyl groups.

ItLe fats according to the invention can be made in a number of different ways. If the second acid is salicylic acid, a suitable method is to neutralize the hydroxy fatty acid and the dicarboxylic acid in at least one rope of the oil together with idthium hydroxide.This neutralization takes place at a temperature of the order of about 82 to 104 ° C. When the soap base has thickened, the temperature is increased to about 127 "WLs 149 ° 0 to bring about dehydration. The soap mass is then ^{cooled to about 88 to 99 0} O and the salicylic acid ester is added. Then more is gradually added Lithium hydroxide is added to convert the salicylate ester to the dilithium salicylate salt. The reaction is carried out at about 14 to 115 ° O, preferably with stirring to facilitate the reaction. In this reaction, the alcohol escapes and the dilithium salicylate is formed. The dehydration then occurs at 14-9 is ⁰ to 16o ° C J completed, whereupon the heated Pett 15 minutes to 193 his 2oo ° C, in order to improve the yield. Then, the Hasse is cooled with additional oil to a product of the desired consistency

2G9822 / 0919

to get .. Instead, the additional oil can also be added to the soap concentrate be added before the formation of the dilithium salicylate takes place in the mass.

Another method is to make all three of them types of acids used to neutralize the fat together or a lower ester of the second type of hydroxy acids, for example methyl salicylate, simultaneously with the neutralization saponify the hydroxy acid of the first type, for example hydroxystearic acid, and the dicarboxylic acid. Another one The process consists in the common neutralization of the hydroxy fatty acid and the ester of the second hydroxy fatty acid followed by Neutralization of the dicarboxylic acid.

If boric acid is used as the third acid, the fat can be produced by neutralizing all three components together or by first neutralizing the mixture of boric acid and hydroxy fatty acid and then the lithium salt the second hydroxycarboxylic acid forms.

example 1

This example illustrates the production of a fat according to the invention on a factory scale in a 4-53 kg kettle. The ingredients used and their proportions are given in Table I below.

Table I.

Parts by weight in percent

Ingredients Ready-made fat base

12-Hydroxyε tearins acid 11.50

Azelaic acid 3 · 97 _o

—Fc> -

(Continuation of Table I)

(c)
Lithium hydroxide monohydrate ^v '3.34

Methyl salicylate 2.85

Li tmum hydroxide monohydrate ^ '1.55

Lube Oil ^ 81.29

(a) A mixture of refined and dewaxed solvent

is paraffin distillate that is hydrofined and has a viscosity of 52o SUS ba 38 ° C and a viscosity index of 93.

(b) 4.5% water and methanol are formed during the reaction of the base with the fatty acids and the methyl salicylate. These are driven off again during the dehydration so that a film yield of 100 % of the finished fat base is obtained.

(c) This part of the LiOH.HgO is only required to

to neutralize the 12-hydroxystearic acid and the azelaic acid.

(d) This part of the LiOH.HpO is required to work with the methyl salicylate to react with the formation of dilithium salicylate.

The 12-hydroxystearic acid and the azelaic acid are poured into the kettle together with about 55% by weight of the base oil, the mixture is heated to 90.5 to 93 ° G until the carboxylic acid has dissolved. While the Kesseltcmperatur is maintained at 93 to 96 ⁰ C, is allowed a hot saturated aqueous solution containing lithium hydroxide sufficient to react with the hydroxy stearic acid and azelaic acid, flow gradually added over a period of 1 hour. If the side

- 9 -209872/0919

When the base mass has reached the desired thick consistency, the temperature is increased to approximately 132 ° C as quickly as the dehydration process will allow. If the dehydration is substantially completed, which is reflected by a rapid rise in temperature to 149 ⁰ C, the soap mass is cooled down to 93 ° 0 by cold water through the boiler · - coat round sends in circulation. Then the methyl salicylate is added and mixed with the soap base at 93 ° C. Following this, the fiest of the lithium hydroxide monohydrate (1.55 % calculated on the weight of the finished fat) is added very gradually in the form of a hot saturated fat. At this stage of the process, the heat input and the mixing speed are increased to speed up the dehydration process, which is carried out at about 100-135 ° C to avoid the accumulation of free water within the kettle. If the entire lithium hydroxide was added and completed the dehydration, which manifests itself by a rapid rise in temperature, is heated, the total fat mass to a temperature of 196 ⁰ C and 15 minutes held at that temperature, to improve the fat structure. The fat mixture is then by letting rapidly to about 149 ⁰ Cabgekühlt to cold water hindurchzirkulieren through the boiler jacket, adding a small amount of oil. After the temperature has ^{dropped to below 149 °} C., the remaining oil is stirred into the fat mass, which is gradually cooled. After the fat base has cooled down to a temperature between 65 and 93 ° G, it is sent through a 100-mesh Tyler sieve (sieve openings 0.149 mm) to complete the production.

The product is a smooth, uniform fat of light yellow Pa / ie ji.it cxiic "Ptne + .- ytion in the unworked state of"■;"·.'> Düi 2i? ^V ' ü. Ik ..... f> stresses was the penetration

- 'Ig -

at 25 ° 0 always nocii 2Jo, it increased after 10,000 times more mechanical Stress to 24o and after 100,000 times stress 251.

example 2

a suitable one for the lubrication of the bearings of a locomotive engine To produce fat, the basic fat mass according to Example 1 was added by simply mixing 0.5% by weight Modified phenyl-alpha-hapthylamine, which acts as an anti-oxidant Means serving. In addition, 3.5% by weight of the base oil described in Table X "and 1.75% by weight of a concentrate added to prevent rust, which was designated as Katriumsulfonat BSN and from 50 wt .-% of a light mineral lubricating oil and 5% by weight of neutral barium dinonyl naphthalene sulfonate duration.

The properties of this fat are shown in! Table II a commercial lithium hydroxystearate fat and compared with another lithium hydroxystearate, the dilithium salicylate and was named DLS-Pett. Commercially available lithium hydroxystearate grease was a commercial product that was sold as The sole thickener contained lithium 12-hydroxystearate. The DLS-Pett also contained lithium-12-hydroxystearate as sole "thickening agent, but an additional 3% by weight of one finely divided preformed dilithium salicylate powder as Antioxidants.

It should be noted that the fat according to Example 2 had a dropping point above 260 ° 0, in comparison with a dropping point; of VI ⁰ G for the usual Libhiuaihyaroxystearatfetb, and ¹ JS ⁰ C ^ eI .'a fat, the powdered dilithium salicylate to. .:.:; üvz ^ ■■■ -. '■'

Table II Comparison of the properties of fats

Product according to Example II Usual DLS grease

Lithium hydroxys are available in fat

oil content in percent by weight
oil viscosity in SUS at 38 ⁰ O
ASTM penetration at 25 ⁰ O

60 operations

5 · οοο work steps

lo, ooo operations

100,000 operations

ASO) M-EoIlenest, 100 hours at a speed of. I60 tours per minute
J ASTM penetration at 25 ° G / adhesion at 25 ° 0

80.1 52o

248 265 265 277 + 28 / passed

Water absorption in the ASTM egg roll test% water absorbed / Δ ASTM penetration at 25 ° / adhesion at 25 ° 0

at 65 o

at 65 O + 58 / passed 54 / + I2 / passed
58 / + 44 / passed

over 26o ° 0

ASTM dropping point
* ASTM pivot bearing, 6 hours at 930

Loss per gram slump test 1.1 / nothing

Oil separation within 30 hours at 100 ° C. in% by weight 1.9 IiLGI spindle life, 1 o.ooo rpm at 149 o / h td. 2,388 Oxidation behavior in the ASTM bomb at 99 ° C, pressure loss in atmospheres after 100 hours.

after 500 hours w Eost-Iest according to ASTM D-1743

Copper corrosion test within 24 hours at loo O * AülTi-Test D-1263-53 T

o, 35

passed

passed 86
485

253

264

82.1 52o

234 25o 25o 3o4

+ 38 / passed + 12o / passed

the

66 / + 1o8 / best. 67 / + 76 / best. 36 / + 92 / best.

2o1 ° 0

0.7 / nothing

1.1

288

o, 35

failed
failed

188 ° C

0.9 / nothing

3.9

1,566

o, 18 ι 0.8

passed

Example 3

Using the procedure of Examples 1 and 2 a grease was prepared similar to that described in Example 2, but using an oil of lower viscosity that was 25o SUS at 38 ° C and a viscosity index of 9o. The composition of this fat in% by weight of the ingredients is given in Table III.

Table III " _OjL GSW »-Τ»

Mineral oil, viscosity index 9o, 25o SUS

at 38 ⁰ G 81, o1

12-hydroxystearic acid 8.77

Azelaic acid 2.67

Methyl salicylate 1, o9

Lithium hydroxide monohydrate 3.21

UaSuI BSN (Eostverhinderer) 1.75

Phenyl-alpha-liaphthylamine (oxidation inhibitor) o, 5o

Melting point depressant (*) 1, oo

* An oil concentrate with 20 % active content of 2 parts of a wax-alkylated najfcfchalins and a part of a methacrylate polymer, which has an alkyl radical with 8 to 12 carbon atoms.

This fat has a dropping point of over 3 ^ 6 C and a penetration of 283 at 25 ° C after 60 times exposure. It has a working range between -4-O ⁰ C and + 2o4 G and successfully passed the copper corrosion test within 24 hours at 100 ° C and the rust test according to ASTM D-I743. The rotation values of this grease at -4o ° C when starting and during the run turned out to be very favorable in comparison with a commercially available grease that has an oil of lower viscosity, namely with a viscosity index of 90 and 2oo SUS

- 13 -

? 09a? 7/0919

38 ° C with a mixed soap made of calcium and lithium 12-hydroxystearate was made. The comparison is shown in Table IV. Taking into account the viscosity of the oil used draws, it is found that the grease according to Example 3 shows excellent properties "in the rotation test.

Table IV

AßTM D-1478 twist test (grams cm at -4o ° 0)

When starting in the company

Grease according to Example 3 8,300 236o

Commercial calcium

Lithium grease 1o, 4oo 3ooo

Example 4 (production of the Pett base)

The example describes the production of an IPett base mass using a molecular ratio of 1 mol of hydroxystearic acid and 0.75 mols of azelaic acid, whereby first a soap concentrate and then a pett is formed. 92 g of 12-hydroxystearic acid and 43.2 g of azelaic acid are dispersed at a temperature of 93 ° O in 300 g of a mineral lubricating oil with a viscosity index of 9o and having a viscosity of 55o SUS at 38 ° C. Then y \, are added 7 g Lithiumhydroxydhydrat (LiOH.H ₂ O) and the Eeaktion at 93 continued to 1'-3 ⁰ O, is dehydrated by heating whereupon the Eeaktionsprodukt av2 14-9 ⁰ O. The free alkali content of the dehydrated product was 0.18%. This showed that that

Neutralization of all carboxyl groups was essentially complete. The temperature of the dehydrated product was increased to 199-2o4 ° C for 30 minutes to improve dispersion. The soap concentrate was then cooled by adding additional oil to give it the desired consistency. The product is designated as a fat base in label Y.

Example 5

To prepare a fat according to the present invention, the same procedure is used as for the soap concentrate according to Example 4 applied. After the soap concentrate at 199 to 2o4 ° C had been treated, 3o, 4 g of Mathylsalicylat and 17 g of lithium hydroxide monohydrate were added at 1o4 ° 0. The reaction was then continued for 1 hour at this temperature. During this reaction, methyl alcohol escaped and the dilithium salicylate was formed within the concentrate. After Dehydration at 149 ° 0, the fat was cooled, then oil was added to achieve the desired consistency. The fat is "designated as fat A in Table V.

Example 6

A second fat was prepared using the fat base according to Example 4 instead of the soap concentrate. In the fat base mass were methyl salicylate and lithium hydroxide monohydrate at 1o4 ° C, in the same way as it is described for the preparation of fat A according to Example 5, for Eeaktion brought. The difference was that the methyl salicylate and lithium hydroxide react in the finished fat base and not in the soap concentrate. The get-

- 15 -

209877/0919

The first product is referred to as fat D ". Comparative example I

The effect of removing the dicarboxylic acid soap from the fat was determined by using a fat corresponding to fats A and D was prepared with the omission of the dilithium azelate. This fat is called fat E.

The properties of the fat base mass and the fat masses A, D and E are summarized in Table V. Breases A and D show both have the same molecular ratio of 1 mole of hydroxy stearic acid, 0.75 moles of azelaic acid and about 0.7 moles of salicylic acid. The data obtained for fat E show that the presence a dicarboxylic acid soap is necessary to achieve a sufficiently fine dilithium silicate within the fat and at the same time ensure that the fat has a drop point of at least 26o ° C.

The static oxidation test for the data given in Table V was carried out in the following manner: 5 grams of the grease to be tested were placed in an open ball bearing known Weight entered, which was then hung in an oven heated to 177 ° C. At certain time intervals that became Ball bearings removed from the oven and reweighed to the Determine weight loss of fat. The results are given in hours for a 35% weight loss.

- 16 2098 ?? / 09 1 p

Table Eiccen.eeh.aiten from Lithiu »—Hvdro tearftt-dilithium — ajzelate — fats

fat

CompositionuiiÄjyiGew · -! Hurry Jithium-12-hydroxystearate

Dilithium azelate

Mineral oil with a viscosity index of

and a viscosity of 55o SUS at 38 ° 0

Dilithium Salicylate (396), within the

Mass made from methyl salicylate

DLS particle size

ASIM fenitrate clay at 25 0 in 1otel mm with 6o-fold use at 1oo, ooo-fold use

-Ti ¹ OTs funct

93.6
45.9 93.6
45.9 93.6
45.9 I02.0 917.0 830.5 917.0 885.0 MMM * 3o.o J2.7 51.0 1056.5 1000.0 I009.2 I0I8.0 nothing Fine Fine Rough 291 3o5
335 3o4 248 199 ⁰ O 274 ⁰ O over 26o ° 0 196 ⁰ O

Static oxidation test

up to a loss of 35% by weight

Hours.

8o

Water resistance in ASSM Ro11ent »st. At SS ⁹ U ft water absorbed / ASSH penetration change at 25 0

oil separation «according to the federal test method 3o ötd. at 100 ° 0 in% by weight of ASIM-Prehlager-3} est . 6 hours at 1o4 ° 0 loss in grams / slump test

0.6 / Niohts 28o

78Z + 32
2.7

1.6 / Nothing

295

Comparative example IA

The preparation of fat D was repeated using the equal amount of each ingredient, with the exception of the dilithium salicylate to the fat base in the form of a finely pre-formed Powder was added with all particles less than 150 microns in size rather than the salicylate in the To let fat form · The comparative fat thus obtained possessed essentially the same consistency as fat D (an ASTM penetration of 300) but had a dropping point of only 19o ° C and only showed in the static oxidation test a service life of 175 hours. These data show that the second acidic component must be part of the thickening system. JIt is desirable but not necessary that it is formed within the mass, but in any case the second acid cannot be added as a pre-formed salt -afterwards the thickening system has already formed.

Example 7

Using the general procedure as described in Example 1, various fat compositions were prepared, in which, on the one hand, smaller molar ratios of dibasic acid and methyl salicylate were used (fat F), while in the other case a dibasic acid with 10 or 13 Carbon atoms was used instead of azelaic acid (fats G and I). The compositions of these fat masses and theirs Properties are summarized in Table VI. An additional fat mass (fat I), in which stearic acid instead of the Hydroxystearic acid was used resulted in a liquid product containing undispersed soap instead of one Fat. Composition J showed that a high dropping point fat was also formed by the formation of dilithium salicylate within of the mixture of salicylic acid instead of methyl salicylate could be obtained.

The data for fats G and H show sebacic acid instead

- 18 -

209877/0919

of azelaic acid »it can be used with satisfactory effect could, but that an acid has 13 carbon atoms in the molecule (Brassylic acid) did not provide fat with a high dropping point,

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209877 / (1919

Comparative example II

When replacing τοη ο, 5 get dilithium salicylate with the same Amount of lithium acetate in fat F, a fat mass was delivered which showed a dropping point of only 216 ° C.

Comparative example III

From 1 hol 12-hydroxystearic acid, ο, 75 get sebacic acid and ο, 8 Get benzoic acid became a fat similar to the fat mass G manufactured. The total amount of oil in fat was $ 8.5% Bas Fett had an ASXM penetration of 336 at 25 ° C and one Drop point of 232 ° G. Compared to the fat G with a dropping point of more than 26o ° C, this shows that the replacement of a non-hydroxylic acid, such as benzoic acid, instead of a hydroxylated acid such as salicylic acid, has the dropping point of the Fat lowers.

Example 8

Using the procedure of Example 6, a fat was made manufactured in which the acids used in a pick ratio of 1 pick 12-hydroxystearic acid, ο, 75 pick azelaic acid and o, 75 Get parahydroxybenzoic acid stood. Part of the Fettgrundaas se according to Example 4 was heated to 82 ° C, then benzoic acid was added with a sufficient amount of lithium hydroxide convert the acid into the dilithium salt. The mix was then heated to 110 ° C for 1/2 hour and then dehydrated at 149 ° C for one hour. The fat showed a dropping point over 26 ° C and had an ASTM penetration of 325 at 25 ° C (according to The penetration was 33o after exposure to 60 times. The total content of thickening mass in the fat was 18.1% by weight.

- 2o 20987 770919

■ - 2ο -

Example 9

A fat was prepared by following the procedure of Example 8 using 0.75 moles of lactic acid in place of parahydroxybenzoic acid. In this case, the fat base was made from an oil with a viscosity index of 87, which had a viscosity of 600 SUS at 38 ° C, instead of the oil with a viscosity of 55o SUS at 38 ° C and a viscosity index of 9o. The total content of thickener in the fat in the form of the lithium salts was 15-3% by weight. The dropping point of the fat was 268 ⁰ O and the fat showed a penetration of 328 at 28 ⁰ O (after 6o exposure the penetration was 332).

Example 1o

A grease was made using a combination of lithium salicylate, lithium 12-hydroxystearate and monolithium borate as thickening agents. The base oil used in making this grease was a solvent made from a refined mid-continental lubricating oil distillate sold under the trademark "Solvent fc 600 Neutral "is known and has a viscosity at 38 ° 0 of about 600 SUS. Methyl salicylate and 12-hydroxystearic acid were added to a portion of this base oil. This mixture was heated. After the melting of the 12-hydroxystearic acid had been observed, the temperature was brought to about 82 to 88 ^° C., then the total amount of lithium hydroxide, which was required for the formation of the various lithium salts, was added in the form of a 10% strength aqueous solution also contained the boric acid used to make the fat. The resulting mixture was stirred up to a final temperature of about 193-199 ° C. Most of the base oil was added and the mixture then cooled to about 121 ° C. Then an anti-oxidant as well as other ingredients, e.g.

- 21 209877/0910

a rust inhibitor, added to the fat. The fat was in it in an ordinary fat mill.

Comparative egg game IY

Using the same procedure as in Example 10, comparative greases were prepared with those in one If the methyl salicylate was omitted, in the other case the boric acid was omitted, and in the third case both the boric acid and the methyl salicylate were omitted.

Each of these fat masses produced according to Example 1o (M and N) and the mass according to Comparative Example 4, with regard to its dropping point and its ASTM penetration at 25 ° C. The composition these fats and their test results are summarized in Table VII below.

- 22 -

2098 ?? / 0919

Composition in percentages by weight Table VII

Fat according to the invention MN

Y comparison greases XYZ

M O «P OO N)

LiOH.H ₂ O 12-hydroxy-stearic acid boric acid

Methyl salicylate base oil

Phenyl-alpha-naphthylamine

NaSuI. BSN

Exam Results

4.0 1.8 12.9 1o.4 1.1 o.5 2.7 0.5 78.3 84.8 1.0 1.0 1.O

Dropping point 25 ⁰ O
unprocessed about 26o ^w c over 26o C ASTM penetration after 6o Bean
judgments 252 275 after I0.000
Stresses 261 28o 293 299

2.5 2.9 1 .8th 12.9 11.5 12th .9 1.1 - - - - 2.5 - - 82.5 81.1 85 .3 1.0 1.0 - - . _in " 1-0

225 ° 0 213 σ 2o7 ° 0 I. cn 262 217 261 7207 255 24o 25o 291 243 277

Claims (8)

Patent claims 1. Air-conditioning oil, which for the most part consists of a lubricating oil and about 2 to 3o wt .- # calculated on the total mass, consists of a thickening system and essentially the following three components contains: (a) a lithium soap of a hydroxy fatty acid with 12 up to 24 carbon atoms, (b) a lithium salt of a second hydroxycarboxylic acid having 3 to 14 carbon atoms in the molecule in which the Hydroxy group sits on a carbon atom that is not more than 6 carbon atoms from the carboxyl group is removed (c) a dilithium salt of a dicarboxylic acid having 4 to 12 carbon atoms in the molecule or (d) a monolithium salt of boric acid, wherein the components (a), (b), (c) are in a weight ratio of about 0.5 to 15 parts by weight of hydroxy fatty acid to a rope of the dicarboxylic acid and a weight ratio of about 0.025 to 2.5 parts of the second Hydroxycarboxylic acid to 1 part of the dicarboxylic acid is retained, while components (a), (b) and (d) are in a weight ratio of about 3 to 100 parts of hydroxy fatty acid to one part of boric acid and a weight ratio of about 0.1 to 1o parts part of the second hydroxycarboxylic acid is boric acid. - 24 - 209822/0919 'V. 2. Hasse according to claim. 1, characterized in that that the ratio of the hydroxy fatty acid with 12 to 24 carbon atoms in the molecule to the weight of the dicarboxylic acid between about 1.5 to 5 wt .-! the former is one part by weight of the latter. r 3. mass according to claims 1 or 2, characterized in that that the quantitative ratio of the hydroxycarboxylic acid having 3 to 14 carbon atoms in the molecule to Weight of the dicarboxylic acid about 0.125 to 1.25 parts by weight the former is one part by weight of the latter. 4. mass according to claims 1 to 3 »characterized in that that the lithium salt of the second hydroxycarboxylic acid is formed within the fat mass. 5. Fat mass according to claims 1 to 4, characterized in that that the second hydroxycarboxylic acid consists of salicylic acid. 6. Fettaas se according to claims 1 to 4, characterized in that that the second hydroxycarboxylic acid is lactic acid or parahydroxybenzoic acid. 7 fat mass according to claims 1 to 6, characterized indicates that the hydroxy fatty acid is a 12-hydroxystearic acid. 8. fat mass according to claims 1 to 7 »thereby marked. indicates that the dicarboxylic acid is azelaic acid or sebacic acid. 209822/0919